Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin)
6,7-Dialkoxy-1-bromomagnesio-2-pivaloyl-tetrahydroisoquinolines (THIQ), prepared as previously described for the unsubstituted reagent, are added to bromo-, methoxy-, and ethoxycarbonyl-substituted benzaldehydes to give 1-hydroxybenzylated THIQs of u-configuration exclusively (2a-4a, 5). These are...
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Swiss Chemical Society
1985-08-01
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| Series: | CHIMIA |
| Online Access: | https://www.chimia.ch/chimia/article/view/9676 |
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| author | Dieter Seebach Isabelle M.P. Huber |
| author_facet | Dieter Seebach Isabelle M.P. Huber |
| author_sort | Dieter Seebach |
| collection | DOAJ |
| description |
6,7-Dialkoxy-1-bromomagnesio-2-pivaloyl-tetrahydroisoquinolines (THIQ), prepared as previously described for the unsubstituted reagent, are added to bromo-, methoxy-, and ethoxycarbonyl-substituted benzaldehydes to give 1-hydroxybenzylated THIQs of u-configuration exclusively (2a-4a, 5). These are converted to the isomeric pivalates either with retention (u-2b-4b) or with inversion of configuration (l-2b-4b). The diastereomers u-3b and l-3b are hydrolized to the free aminoalcohols (3, R1 = R2 = H) which are N-methylated (→3, R1 = CH3, R2 = H) and cyclized photochemically to the known alkaloids (±)-ushinsunine (u-6) and (±)-oliverolin (l-6), respectively. – The highly functionalized, diastereomerically pure 1-hydroxybenzylated THIQ derivatives described here are versatile precursors for the syntheses of aporphine (see 6), protoberberine, quettamine, and phthalid (see 5) alkaloids.
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| format | Article |
| id | doaj-art-b698f44e72d24873af06833367807de3 |
| institution | Kabale University |
| issn | 0009-4293 2673-2424 |
| language | deu |
| publishDate | 1985-08-01 |
| publisher | Swiss Chemical Society |
| record_format | Article |
| series | CHIMIA |
| spelling | doaj-art-b698f44e72d24873af06833367807de32025-08-20T03:53:33ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24241985-08-01397-810.2533/chimia.1985.233Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin)Dieter Seebach0Isabelle M.P. Huber1Laboratorium für Organische Chemie Eidgenössische Technische Hochschule Zürich ETH-Zentrum, Universitätstrasse 16, CH-8092 ZürichLaboratorium für Organische Chemie, Eidgenössische Technische Hochschule Zürich, ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich 6,7-Dialkoxy-1-bromomagnesio-2-pivaloyl-tetrahydroisoquinolines (THIQ), prepared as previously described for the unsubstituted reagent, are added to bromo-, methoxy-, and ethoxycarbonyl-substituted benzaldehydes to give 1-hydroxybenzylated THIQs of u-configuration exclusively (2a-4a, 5). These are converted to the isomeric pivalates either with retention (u-2b-4b) or with inversion of configuration (l-2b-4b). The diastereomers u-3b and l-3b are hydrolized to the free aminoalcohols (3, R1 = R2 = H) which are N-methylated (→3, R1 = CH3, R2 = H) and cyclized photochemically to the known alkaloids (±)-ushinsunine (u-6) and (±)-oliverolin (l-6), respectively. – The highly functionalized, diastereomerically pure 1-hydroxybenzylated THIQ derivatives described here are versatile precursors for the syntheses of aporphine (see 6), protoberberine, quettamine, and phthalid (see 5) alkaloids. https://www.chimia.ch/chimia/article/view/9676 |
| spellingShingle | Dieter Seebach Isabelle M.P. Huber Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) CHIMIA |
| title | Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) |
| title_full | Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) |
| title_fullStr | Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) |
| title_full_unstemmed | Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) |
| title_short | Herstellung diastereomerenreiner l- oder u-konfigurierter 1-hydroxybenzylierter Tetrahydroisochinolin-Vorläufer für Aporphin-, Protoberberin-, Quettamin- und Phthalid-Alkaloide (Stereoselektive Synthese von (±)-Ushinsunin und (±)-Oliverolin) |
| title_sort | herstellung diastereomerenreiner l oder u konfigurierter 1 hydroxybenzylierter tetrahydroisochinolin vorlaufer fur aporphin protoberberin quettamin und phthalid alkaloide stereoselektive synthese von ushinsunin und oliverolin |
| url | https://www.chimia.ch/chimia/article/view/9676 |
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